CN105051441A - Heat-insulating molding compound, heat-insulating molded article, and production method for same - Google Patents
Heat-insulating molding compound, heat-insulating molded article, and production method for same Download PDFInfo
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- CN105051441A CN105051441A CN201480011428.4A CN201480011428A CN105051441A CN 105051441 A CN105051441 A CN 105051441A CN 201480011428 A CN201480011428 A CN 201480011428A CN 105051441 A CN105051441 A CN 105051441A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
- F16L59/04—Arrangements using dry fillers, e.g. using slag wool which is added to the object to be insulated by pouring, spreading, spraying or the like
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
- F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
- F16L59/028—Composition or method of fixing a thermally insulating material
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/159—Coating or hydrophobisation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
Abstract
The invention provides a heat-insulating molding compound with which heat-insulating molded articles of high strength and exceptional heat insulating properties can be produced. The compound is formed by crushing aerogel particles (A) coated with an adhesive (4).
Description
Technical field
The present invention relates to based on the adiabatic moulding material of aerogel particle, adiabatic formed body and their preparation method.
Background technique
As heat insulator, there will be a known foamed material, such as polyurethane foam and phenol formaldehyde foam (foaming base heat insulator).The heat-insulating property of described foamed material performance is because of the air bubble produced that foams.But this type of polyurethane foam and phenol formaldehyde foam have the thermal conductivity higher than air thermal conductivity usually.Therefore, it is favourable for making the thermal conductivity of heat insulator be less than air thermal conductivity for improving heat-insulating property further.Be less than the method for air thermal conductivity as acquisition thermal conductivity, there will be a known the method using and there is the air gap of the filled with foaming material (such as polyurethane foam and phenol formaldehyde foam) such as the gas (such as chloro-fluoro-hydrocarbons) of lower thermal conductivity.But, there are misgivings by the method for gas filling air gap and be: As time goes on, blanketing gas may leak out from air gap, and it may cause the increase of thermal conductivity.
In recent years, the method for improving heat-insulating property based on vacuum has been proposed.In these methods, such as, the porous material of such as calcium silicate and/or glass fibre is used, and under they are maintained at the vacuum state of about 10Pa.But the insulation method based on vacuum needs to keep vacuum state, therefore has the problem of deterioration and preparation cost in time.In addition, based in the heat insulator of vacuum, because it needs to keep vacuum state, the shape of heat insulator can be restricted, and therefore its application is also subject to strict restriction.Due to these reasons, the described heat insulator based on vacuum is restricted in actual applications.
By the way, the thin block of known porous silica (so-called aerogel) is as the material of heat insulator, and it shows the thermal conductivity lower than the air thermal conductivity under normal pressure.This material can obtain based in such as method disclosed in US4402927, US4432956 and US4610863.According to these methods, aerosil is prepared as raw material by using alkoxy silane (it is also referred to as " silicon alkoxide " and " alkyl silicate ").Specifically, described aerosil obtains as follows: hydrolyzable alkoxy TMOS in the presence of the solvent, to prepare the compound with the wet gelatine of silicon dioxide skeleton of the result as polycondensation; And the compound of dry described wet gelatine under the super critical condition of transition point being not less than described solvent.As described solvent, such as, alcohol, liquefied carbon dioxide etc. can be used.Aerogel particle, it is the granular material of described aerogel, has the thermal conductivity lower than air thermal conductivity, is therefore used as the raw material of heat insulator.
Reference
Patent documentation
Patent documentation 1:US4402927
Patent documentation 2:US4432956
Patent documentation 3:US4610863
Summary of the invention
Technical problem
But, because described aerogel particle weight is very light, intensity difference and frangible, therefore, be difficult to process aerogel particle.In addition, because described aerogel particle itself is fragility, the heat insulator formed by aerogel particle molding has poor intensity, is easy to cracking and breakage.In order to increase the intensity of heat insulator, reinforcing material etc. can be added or increase the amount of tackiness agent, but in this case, the reinforcing material added or the increasing amount of tackiness agent may cause the reduction of the heat-insulating property of heat insulator.In view of the foregoing, exist the intensity by increasing aerogel particle and moulding article thereof and prevent heat-insulating property from reducing simultaneously and realize the demand of the heat insulator of the requirement to enough intensity and heat-insulating property simultaneously.
Consider above-mentioned situation and complete the present invention, the object of this invention is to provide the adiabatic formed composite material for the preparation of adiabatic formed body, its intensity is higher and heat-insulating property excellent; There is provided intensity higher and the adiabatic formed body of heat-insulating property excellence; And prepare the method for this adiabatic formed body.
Solution
The aerogel particle preparation of tackiness agent is coated with according to thermal insulation shaping (compound) material piece according to the present invention by fragmentation.
Adiabatic formed body according to the present invention is formed by described thermal insulation shaping (compound) material piece molding.
Preparation method according to adiabatic formed body of the present invention comprises: with tackiness agent coated gas gel particle to prepare the aerogel particle of coating, the aerogel particle of broken described coating, thus obtain adiabatic (compound) material piece that is shaped, and adiabatic (compound) material piece that is shaped described in molding.
Beneficial effect of the present invention
According to the present invention, can obtain adiabatic formed body, its intensity is higher and have excellent heat-insulating property.
Accompanying drawing explanation
Figure 1A is the schematic diagram of the step of the embodiment of the method illustrated for the preparation of adiabatic moulding material sheet;
Figure 1B is the schematic diagram of another step of the embodiment of the described method illustrated for the preparation of adiabatic moulding material sheet;
Fig. 1 C is the schematic diagram of another step of the embodiment of the described method illustrated for the preparation of adiabatic moulding material sheet;
Fig. 1 D is the enlarged diagram of the inside that adiabatic formed body is described;
Fig. 2 A is the schematic diagram of a step of the embodiment of the method illustrated for molded insulation formed body;
Fig. 2 B is the schematic diagram of another step of the embodiment of the described method illustrated for molded insulation formed body;
Fig. 2 C is the schematic diagram of another step of the embodiment of the described method illustrated for molded insulation formed body;
Fig. 2 D is the schematic diagram of another step of the embodiment of the described method illustrated for molded insulation formed body;
Fig. 3 A is the schematic diagram of the example of aerogel particle;
Fig. 3 B is the schematic diagram of another example of aerogel particle;
Fig. 3 C is the schematic diagram of another example of aerogel particle; With
Fig. 4 is the electron micrograph of aerogel particle.
Specific embodiments
Hereafter specific embodiment of the invention scheme will be described.
Aerogel is porous material (porous body), and it is obtained to make gas displacement be included in the solvent in gel by desiccant gel.The granular material of aerogel is called as aerogel particle.The known embodiment of aerogel comprises aerosil, carbon aerogels and alumina aerogels, wherein preferably uses aerosil.Aerosil has excellent heat-insulating property, be easy to preparation, and preparation cost is low, therefore easy acquisition compared with the aerogel of other type.It should be noted that the result of volatilizing completely as the solvent in gel and the cancellated material had containing air gap prepared also can be called as " xerogel ", the aerogel in this specification can comprise xerogel.
Fig. 3 A to Fig. 3 C shows the schematic diagram of the example of described aerogel particle A.As shown in figures 3 a and 3b, aerogel particle A is silica aerogel particles, and is the silica (SiO with the hole being of a size of about tens nanometer (such as in the scope of 20-40nm)
2) structure.This aerogel particle A obtains by supercritical drying etc.Aerogel particle A is made up of particulate P (silicon dioxide microparticle), and they are bonded to each other to form three-dimensional netted shape.A kind of size of silicon dioxide microparticle is: such as about 1-2nm.As shown in FIG. 3 C, gas G is allowed to enter the hole that aerogel particle A is of a size of about tens nanometer.These holes block the transmission of constituent of air (as nitrogen and oxygen), therefore likely thermal conductivity are reduced to the degree being less than air thermal conductivity.Such as, thermal conductivity (WLF) λ that the conventional heat insulator being provided with air has is 35-45mW/mK, but by aerogel particle A, thermal conductivity (WLF) λ of heat insulator can be reduced to about 9-12mW/mK.Usually, aerogel particle A has hydrophoby.Such as, in the silica aerogel particles shown in Fig. 3 B, most silicon atom (Si) is bonded to (one or more) alkyl group (methyl group, CH
3), a few keys in them is incorporated into (one or more) oh group (OH).Therefore, this particle has relatively low surface polarity.
Fig. 4 is the electron micrograph of silica aerogel particles.This silica aerogel particles is obtained by supercritical drying.Can recognize from this photo, silica aerogel particles has 3 D stereo reticular structure.Typically, the silicon dioxide microparticle that the reticular structure of aerogel particle A is less than the linear combination of 10nm by size is formed.It should be noted that described reticular structure can have the smeared out boundary between particulate P, and described cancellated some parts can be formed by the silicon dioxide structure (-O-Si-O-) extended linearly.
Aerogel particle A for adiabatic formed body has no particular limits, and can use the aerogel particle obtained by the preparation method commonly used.The representative instance of aerogel particle comprises: the aerogel particle A obtained by supercritical drying and the aerogel particle A obtained based on liquid glass.
The silica aerogel particles obtained by supercritical drying can obtain as follows: by preparing silica dioxide granule with the sol-gel process polymer raw of liquid phase reaction method; And remove its solvent by supercritical drying.Such as, alkoxy silane (it is also referred to as " silicon alkoxide " or " alkyl silicate ") is used as raw material.Alkoxy silane is hydrolyzed in the presence of the solvent, to generate the compound with the wet gelatine of silicon dioxide skeleton as polycondensation result, then, the compound of wet gelatine is dry at supercritical conditions, and temperature and pressure is wherein equal to or greater than the temperature and pressure of the transition point of solvent.Solvent can be alcohol, liquefied carbon dioxide etc.According to the drying of the gel compound under super critical condition, its solvent is removed, and the reticular structure of gel is kept simultaneously, and result to obtain aerogel.Aerogel particle A, it is the granular material of aerogel, by the gel powder comprising solvent is broken into particle, then can carrys out the dry particle comprising the gel of solvent by supercritical drying and obtain.Alternately, aerogel particle A obtains by the blocks pulverizing the aerogel obtained as supercritical drying result.
Alkoxy silane as the raw material of aerogel particle A is not particularly limited, and can be dual functional alkoxy silane, the alkoxy silane of trifunctional, the alkoxy silane of four senses or their combination.The example of dual functional alkoxy silane comprises dimethyldimethoxysil,ne, dimethyldiethoxysilane, diphenyl diethoxy silane, dimethoxydiphenylsilane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxysilane, diethyldiethoxysilane and diethyldimethoxysilane.The example of the alkoxy silane of trifunctional comprises MTMS, MTES, ethyl trimethoxy silane, ethyl triethoxysilane, phenyltrimethoxysila,e and phenyl triethoxysilane.The example of the alkoxy silane of four senses comprises tetramethoxy-silicane and tetraethoxysilane.Two (trimethyl silyl) methane, two (trimethyl silyl) ethane, two (trimethyl silyl) hexane or vinyltrimethoxy silane can be used as alkoxy silane.The partial hydrolysate of alkoxy silane can be used as described raw material.
Preferably, the hydrolysis of alkoxy silane and polycondensation are carried out in presence of water, and more preferably carry out under the existence of the mixing material of water and organic solvent, alkoxy silane is solvable in described organic solvent, and described organic solvent is compatible with water.Use this mixed solution to make it possible to the process that is hydrolyzed continuously and polycondensation process as solvent, therefore can obtain gel expeditiously.In this process, because the material (wet gel) of gelatine is present in the solvent as dispersion medium, thus polymer is created.That solvent solvable and compatible with water has no particular limits wherein for alkoxy silane.The example of this solvent comprises: alcohol, such as methyl alcohol, ethanol, propyl alcohol, isopropanol and butanols; Acetone and DMF.These materials can be used alone or combinationally use.
Also preferably the hydrolysis of alkoxy silane and polycondensation are carried out in the presence of a catalyst, and described catalyzer causes removing alkoxy base from alkoxy silane, to promote condensation reaction.The example of this catalyzer comprises acidic catalyst and base catalyst.Particularly, the example of described acidic catalyst comprises hydrochloric acid, citric acid, nitric acid, sulfuric acid and ammonium fluoride.The example of described base catalyst comprises ammonia and piperidines.
Suitable component be introduced in the reaction liquid of alkoxy silane.The example of this component can comprise surface active agent (surface-activatingagent) and functional group's derivant (functionalgroupinductionagent).This annexing ingredient can provide favourable function for aerogel particle A.
Aerogel can be obtained by the wet gel obtained with supercritical drying drying.Preferably, described wet gel is first cut or pulverize as particle, and to prepare the particle of the gel comprising described solvent, then the particle of gel is dry by supercritical drying.By doing like this, aerogel can be made into particle, and dried, and aerogel structure can not be made to break, and therefore aerogel particle A can easily obtain.In this case, the uniform gel particle of preferred preparation size, and this makes the uniform particle sizes of aerogel particle A.Alternately, aerogel particle A, by preparing Monolithic aerogel, is then obtained by the blocks of reducing mechanism pulverizing aerogel.The aerogel particle A obtained can sieve or classification, to obtain size evenly aerogel particle.When the size of aerogel particle A is by homogenization, operability can improve, and can easily obtain stable product.
The aerogel particle A obtained based on liquid glass can be prepared by atmosphere pressure desiccation, and described method order comprises following process: the crushing process of the preparation process of Ludox, the gelatinization process of Ludox, maturing process, gel, solvent replacement process, hydrophobic process and Dry run.Liquid glass can be the high concentration solution of the mineral silicate of such as sodium silicate usually, and can by being such as dissolved in the water by mineral silicate and being heated and obtaining.
The raw material of Ludox can be silicon alkoxide, alkali-metal silicate etc.The example of silicon alkoxide comprises tetramethoxy-silicane and tetraethoxysilane.The alkoxy silane described in about the explanation of supercritical drying can be used as described silicon alkoxide.Alkali-metal silicate can be potassium silicate, sodium silicate etc.The alkali-metal silicate of preferred use, because it is cheap; And more preferably use sodium silicate, because it is easy to obtain.
When using alkali-metal silicate, Ludox can by using the method for carrying out depickling with the inorganic acid of all example hydrochloric acids and sulfuric acid, or use has H
+prepared by the method for the cation exchange resin of gegenion.In these methods, preferably cation exchange resin is used.
By making the solution of the alkali-metal silicate with debita spissitudo by being filled with the packed layer of cation exchange resin, Ludox can be prepared by using acid type cation exchange resin.Alternately, Ludox can be prepared as follows: introduced by cation exchange resin in the solution of alkali-metal silicate; Mixed; Removing alkali metal; Then cation exchange resin is filtered by such as crossing.The amount of cation exchange resin is preferably not less than the amount needed for alkali metal exchanging and comprise in a solvent.Solvent stands dealkalization (demetalization) by cation exchange resin.
Acid type cation exchange resin can be polystyrene, acrylic acid series or methacryl system, and such as has the sulfonic group of displacement or carboxylic group as ion-exchange group.Wherein, the so-called strongly acidic cation-exchange with sulfonic group is preferably used.The cation exchange resin exchanged for alkali metal can recycle after the regenerative process passed therethrough with sulfuric acid or hydrochloric acid.
After this, the silicon dioxide gel prepared by gelling, then by its slaking.In gelatinization and maturing process, preferably control its pH value.Usually, adopt the silicon dioxide gel after the ion exchange process of cation exchange resin to have relatively low pH value, such as 3 or less.When neutralizing this silicon dioxide gel to make its pH within the scope of subacidity to neutral pH, silicon dioxide gel is by gelatine.By controlling its pH scope to 5.0-5.8, and preferably can carry out gelling silicon dioxide gel in the scope of 5.3-5.7.Its pH can be controlled by interpolation alkali and/or acid.Described alkali can be ammoniacal liquor, sodium hydroxide, caustic potoash, alkali-metal silicate etc.Described acid can be hydrochloric acid, citric acid, nitric acid, sulfuric acid etc.The gel slaking at steady-state that pH is controlled.Maturing process can carry out 4-24 hour in the temperature range of 40-80 DEG C.
Preferably, after maturing process, gel is pulverized.The aerogel particle A of expectation is easily obtained by pulverizing gel.Such as, the carrying out of the crushing process of gel can be by: gel is put into Henshall type mixer or colloidal sol described in mixer gelling; And with the period that suitable rotational speed operation one section, mixer is suitable.
After crushing process, preferably carry out solvent replacement process.In solvent replacement process, the solvent (such as water) for the preparation of gel is replaced as has little capillary another kind of solvent, and dry contraction occurs during to avoid gel dried.Solvent replacement process generally includes multiple step, and preferred two steps, because being difficult to directly be replaced as by water has little capillary solvent.The criterion of the solvent being used for first step is selected to comprise: to have and water and the good compatibility with the solvent for second step.Can be methyl alcohol, ethanol, isopropanol, acetone etc. for the solvent in first step, and ethanol be preferred.The criterion of the solvent being used for second step is selected to comprise: to have the lower reactivity with the primer used in follow-up hydrophobic process; And there is little surface tension, thus cause less drying to be shunk.Can be hexane, dichloromethane, methyl ethyl ketone etc. for the solvent in second step, and hexane be preferred.As required, additional solvent swap step can be carried out between the first solvent swap step and the second solvent swap step.
After solvent replacement process, preferably carry out hydrophobization process.Alkylalkoxy silane, haloalkyl silane etc. can be used as the primer in described hydrophobization process.Such as, can preferably use dialkyldichlorosilan,s or monoalkyltrichlorosi,ane, and, consider reactivity and cost of material, more preferably use dimethyldichlorosilane.Hydrophobization process can be carried out before solvent replacement process.
After hydrophobization process, be separated from solvent by the gel obtained by filtering, then detergent gel is to remove unreacted primer.After this, by gel drying.Dry run can be carried out at ambient pressure, and can carry out under heating and/or hot air.Preferably in inactive gas (such as nitrogen) atmosphere, carry out Dry run.According to this process, the solvent in gel is removed from gel, thus aerogel particle A can be obtained.
The aerogel particle A obtained by supercritical drying and there is identical structure substantially based on the aerogel particle A that liquid glass obtains.Also namely, they have granular structure separately, and wherein silicon dioxide microparticle combines, thus form three-dimensional netted shape.
Shape for aerogel particle A has no particular limits, and it can be one of various shape.Under normal circumstances, the aerogel particle A obtained by above-mentioned method has uncertain shape, because aerogel particle A experiences crushing process etc.Can say, they can have the rock-like of irregular surface.They also can be spherical, rugby shape, plate shape, slice-shaped, fiber shape etc.Aerogel particle A for molding can be the mixture of the particle with different-grain diameter.In layered product, particle is adhering to each other and integrated, and therefore aerogel particle A not necessarily has uniform size.About the size of aerogel particle A, consider intensity, operability and formability, the number of preferably excessive particle and too small particle is less.Specifically, the Mean particle diameter of aerogel particle A preferably falls in the scope of 100 μm of-5mm, and more preferably falls in the scope of 500 μm of-1.5mm.In this manual, Mean particle diameter refers to the particle size values being positioned at 50% place in the accumulation domain size distribution measured by laser diffraction and scattering method.
Then, be described to preparation according to the method for adiabatic formed body B of the present invention.This method comprises: with the first step (Figure 1A and Figure 1B) of the outer surface of tackiness agent 4 coated gas gel particle A; The second step (Figure 1B and Fig. 1 C) of the aerogel particle A of tackiness agent 4 is coated with, to obtain adiabatic moulding material C sheet for fragmentation; And the third step of molded insulation moulding material C sheet (Fig. 1 C and Fig. 1 D).
In a first step, as shown in Figures 1 A and 1 B 1, in order to tackiness agent 4 coated gas gel particle A, common granulator or common coating apparatus can be used.Such as, the type of often kind of device can be rotatable container type, rotating knife flap-type, fluid type etc.Above-mentioned any type can be selected according to by the tackiness agent 4 of use.Then, be placed in device as above by the water of the aerogel particle A of prearranging quatity, tackiness agent 4 and necessity, they are mixed reaches predetermined time, then dry, can obtain the aerogel particle A being coated with tackiness agent 4 thus.
No matter thermoplastic resin or thermosetting resin, or all can be used as tackiness agent 4 both them.The example of thermoplastic resin comprises acrylic resin, polyethylene resin, acrylic resin, polystyrene resin, nylon resin etc.These resins can be used alone or in combination.The example of thermosetting resin comprises phenolic resin, melamine resin, polyurethane resin, epoxy resin, silicone etc.These resins can be used alone or in combination.
Preferably, described aerogel particle A 50% or more outer surface be preferably coated with tackiness agent 4, and the outer surface being more preferably 80% or more (upper limit is 100%) is coated with tackiness agent 4.
The thickness of the tackiness agent 4 of coated gas gel particle A preferably falls in the scope of 0.1 μm-50 μm, and more preferably falls in the scope of 0.5 μm-10 μm.
Content for the tackiness agent 4 in adiabatic formed body B has no particular limits, but such as it falls in the scope of the 5-50 quality % of the total amount of adiabatic formed body B.
In the second step, as shown in figures 1 b and 1 c, in order to fragmentation is coated with the aerogel particle A of tackiness agent 4, general disintegrator can be used.Specifically, disintegrator can be: such as tumbling mill, hammer mill, roll mill, pebble mill, jet mill etc.Adiabatic moulding material C sheet in fig. 1 c can obtain by being coated with the aerogel particle A of tackiness agent 4 by above-mentioned crusher in crushing.In this case, do not require that all aerogel particle A being coated with tackiness agent 4 are broken, but require that a part at least is wherein broken.Preferably, more than the 60 quality % being coated with the total amount of the aerogel particle A of tackiness agent 4 can be broken, and more preferably, the aerogel particle A in the scope of 60-90 quality % can be broken.As the result of fragmentation, form at least some adiabatic moulding material C sheet, uncoated have the surface of the aerogel particle A of tackiness agent 4 to be again exposed.Preferably, relative to the Mean particle diameter of the not yet broken aerogel particle A as raw material, the Mean particle diameter of adiabatic moulding material C falls in the scope of its 1/10-1/2 (comprising the thickness of tackiness agent 4).Mean particle diameter due to adiabatic moulding material C is 1/10 of the Mean particle diameter of aerogel particle A or more, can suppress the weakening of operability and moldability.Because the Mean particle diameter of adiabatic moulding material C is 1/2 or following of the Mean particle diameter of aerogel particle A, so-called heat bridge is more not easily formed, and it can suppress the weakening for heat-insulating property.
Then, in third step, as shown in Fig. 1 C and Fig. 1 D, in order to molded insulation moulding material C, molding methods can be: such as compression molding, transfer molding, injection-molded, extrusion molding etc.Any above-mentioned molding methods can be selected according to the shape of the tackiness agent 4 that will use and the adiabatic formed body B that will prepare.
The example of third step is shown in Fig. 2 A to Fig. 2 D.First, adiabatic moulding material C sheet is uniformly mixed in bottle 5 if desired.Then, press 30 is used to the molding of adiabatic moulding material C.Described press 30 comprises dip mold 31 and top die 32.
Then, as shown in Figure 2 A, sidewall mould 31b is attached to dip mold 31, to form recess 31a.Stripping film 34 is placed on the bottom surface of recess 31a, then surficial sheets 6 is put thereon.Then, adiabatic moulding material C sheet is incorporated into the recess 31a above dip mold 31 from described bottle 5.Now, preferred described dip mold 31 is preheating to not higher than the solidifying temperature of tackiness agent 4 by heating.
Then, as shown in Figure 2 B, the end face of the adiabatic moulding material C sheet of introducing is flattened instrument 33 and flattens, such as spoon, blade etc.After this, another sheet surficial sheets 6 is placed on the adiabatic moulding material C sheet that end face is flattened, and after this places another sheet stripping film 34 thereon.
After this, top die 32 is introduced recess 31a from upside, then suppress by heat and pressure, as shown in FIG. 2 C.By this compacting, tackiness agent 4 shows bond properties, thus adiabatic moulding material C sheet is by bonding integration.In addition, by the bonding of tackiness agent 4, each surficial sheets 6 is bonded to adiabatic moulding material C sheet, and therefore surficial sheets 6 is integrated with the layered product of adiabatic moulding material C.After having suppressed, products obtained therefrom is therefrom taken out, and dry by dryer.
Consequently, the adiabatic formed body B be made up of the moulding article of adiabatic moulding material C (aerogel layer A3) and surficial sheets 6 is obtained, as illustrated in fig. 2d.It should be noted that the adhesiveness for strengthening surficial sheets 6 and aerogel layer A3, additional tackiness agent 4 be directed into the interface between uncured aerogel layer A3 and surficial sheets 6.
Adiabatic formed body B as above is formed as the thermal shield of shape as plate.It should be noted that adiabatic formed body B can be formed as the shape except tabular by adopting the moldings such as suitable molding tool.Described adiabatic formed body B has following structure, and wherein, surficial sheets 6 is placed on the apparent surface of the aerogel layer A3 formed by the adiabatic moulding material C sheet bonded respectively.By with surficial sheets 6 coating gas gel layer A3, the intensity of adiabatic formed body B can be improved.Such as, the fibre sheet material etc. of resin sheet, fibre sheet material, resin-dipping can be used as surficial sheets 6.When surficial sheets 6 is containing resin, by with the resin-bonding of surficial sheets 6 and integrated surficial sheets 6 and aerogel layer A3, likely improve the adhesiveness of aerogel layer A3 and surficial sheets 6 further.It should be noted that surficial sheets 6 can only be placed on a surface of aerogel layer A3.Adiabatic formed body B also by thereon not the aerogel layer A3 of placement surface sheet material 6 form.But preferred surface sheet material 6 is placed on the apparent surface of aerogel layer A3, to gain in strength.
For the adiabatic formed body B as shown in figure ip obtained by said method, the partial outer face of adiabatic moulding material C sheet is uncoated tackiness agent 4.Therefore, the existence of tackiness agent 4 is discontinuous.Because the thermal conductivity of tackiness agent 4 is good, so-called heat bridge may be formed.But, the formation of heat bridge can suppress by the tackiness agent 4 of existence discontinuous in aerogel layer A3.Consequently, superior heat-insulating property can be obtained.It should be noted that adiabatic moulding material C sheet is sequentially placed so that illustrate in Fig. 1 D, but in the adiabatic formed body B of reality, adiabatic moulding material C sheet is placed in unordered mode usually.
In addition, although a part for adiabatic moulding material C sheet may not be coated with by tackiness agent 4, adiabatic moulding material C sheet can be adhered to mutually by the tackiness agent 4 of the remainder of coated insulation moulding material C sheet, therefore, can obtain higher intensity.According to the present invention, intensity can be obtained higher and there is the adiabatic formed body B of excellent heat-insulating property.Described adiabatic formed body B can be suitable as structural material etc.
Embodiment
Hereinafter, reference example is specifically described the present invention.
The preparation method of aerogel particle
Prepare tetramethoxy-silicane oligomer (" methyl silicate 51 ", purchased from COLCOATCO., Ltd., its mean molecule quantity is 470) as alkoxy silane, ethanol (special grade chemical, purchased from nacalaitesqueinc.) and water as solvent, and the ammoniacal liquor of 0.01mol/l is as catalyzer.1mol tetramethoxy-silicane oligomer, 120mol ethanol, 20mol water and 2.16mol ammoniacal liquor are mixed, to prepare the reaction liquid of colloidal sol shape.
After this, the reaction liquid of colloidal sol shape is put into bottle, then place gelatine at normal temperatures, to produce the compound of gelatine.
Then, the compound of above-mentioned gelatine is put into the temperature being filled with liquefied carbon dioxide is 18 DEG C, pressure is 5.4MPa (55kgf/cm
2) Pressure Container in, and be that carbon dioxide reaches three hours by the ethanol replacement in the compound of gelatine.After this, regulate the temperature and pressure of the inside of Pressure Container, to meet the super critical condition of carbon dioxide, its temperature is 80 DEG C and pressure is 16MPa (160kgf/cm
2), then remove solvent and reach 48 hours.Using 0.3mol/l HMDS as in the atmosphere under hydrophobizers adds super critical condition, described hydrophobizers disperses two hours in supercritical fluid, and the compound of gelatine is held in supercritical fluid, so that hydrophobic.After this, discharge supercritical carbon dioxide and reduce the pressure of internal tank, thus ethanol and hydrophobizers being removed from the compound of gelatine.15 hours are lasted altogether to the end time of decompression from the elapsed time adding described hydrophobizers.Aerogel particle (silica aerogel particles) is taken out by from Pressure Container.Silica aerogel particles has 0.086g/cm
3bulk density and the Mean particle diameter of 700 μm.
The spraying method of tackiness agent
Prepare the phenolic resin (" commercial Application phenol SP1103 " as tackiness agent, purchased from ASAHIORGANICCHEMICALSINDUSTRYCO., and acrylic resin (" VINYBLAN2687 ", purchased from SHIN-ETSUCHEMICALCO., LTD.) LTD.).
Then, 8.5g aerogel particle, 0.75g phenolic resin, 2.5g acrylic resin and 3g water are placed in spinning container type coating apparatus (" RockingMixerRM-10 ", purchased from AICHIELECTRICCO., LTD.), stir 10 minutes, then dry.Thus, the aerogel particle that is coated with tackiness agent of acquisition.Relative to the aerogel particle obtained by this way, 80% or more of the outer surface of adhesive coverage aerogel particle.It should be noted that the thickness of the tackiness agent of coated gas gel particle is 1 μm.
The breaking method of aerogel particle
The aerogel particle tumbling mill (" EXAKTM-50 ", purchased from NAGASESCREENPRINTINGRESEARCHCO., LTD.) being coated with tackiness agent is broken, obtains adiabatic moulding material sheet thus.The Mean particle diameter of adiabatic moulding material is about 300 μm.
The molding methods of adiabatic moulding material
Adiabatic moulding material sheet mixes equably in bottle.After this, be 180 DEG C by die temperature and pressing time is the molding under the condition of 20 minutes, with mixing tab described in press molding, the adiabatic formed body of preparation tabular.The thermal conductivity of the adiabatic formed body obtained by this way is 0.016W/mK.The measurement of thermal conductivity carries out according to " the JISA1412-1 test method of thermal resistance and adiabatic relevant nature ".It should be noted that the intensity of adiabatic formed body is enough to be used as structural material etc., particularly, the intensity measured by three-point bend test is 0.06MPa.Three-point bending strength is measured according to " mensuration of JISK7221-2 form rigid cellular plastic bending properties ".
Comparative example 1
The preparation method of aerogel particle
Prepared by aerogel particle mode in the same manner as in Example 1.
Tackiness agent spraying method
The aerogel particle being coated with tackiness agent obtains by mode in the same manner as in Example 1.
The molding methods of aerogel particle
The not broken aerogel particle being coated with tackiness agent, the aerogel particle being coated with tackiness agent uses press molding under molding temperature is 180 DEG C and pressing time is the condition of 20 minutes, thus the adiabatic formed body of preparation tabular.Measured by three-point bend test, the intensity of the adiabatic formed body obtained by this way is 0.06MPa.The thermal conductivity of described adiabatic formed body is 0.017W/mK.
Description of reference numerals
A: aerogel particle
B: adiabatic formed body
C: adiabatic moulding material
4: tackiness agent
Claims (3)
1. adiabatic moulding material sheet, it is coated with the aerogel particle of tackiness agent by broken and prepared.
2. adiabatic formed body, it is obtained by molding each adiabatic moulding material sheet according to claim 1.
3. the preparation method of adiabatic formed body, it comprises:
With tackiness agent coated gas gel particle, to prepare the aerogel particle of coating;
The aerogel particle of broken described coating, to obtain adiabatic moulding material sheet; With
Adiabatic moulding material sheet described in molding.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-041081 | 2013-03-01 | ||
| JP2013041081 | 2013-03-01 | ||
| PCT/JP2014/001072 WO2014132655A1 (en) | 2013-03-01 | 2014-02-27 | Heat-insulating molding compound, heat-insulating molded article, and production method for same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105051441A true CN105051441A (en) | 2015-11-11 |
Family
ID=51427930
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480011428.4A Pending CN105051441A (en) | 2013-03-01 | 2014-02-27 | Heat-insulating molding compound, heat-insulating molded article, and production method for same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20160010786A1 (en) |
| EP (1) | EP2963327A4 (en) |
| JP (1) | JPWO2014132655A1 (en) |
| CN (1) | CN105051441A (en) |
| WO (1) | WO2014132655A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150050816A1 (en) * | 2013-08-19 | 2015-02-19 | Korea Atomic Energy Research Institute | Method of electrochemically preparing silicon film |
| US10633915B2 (en) | 2013-12-19 | 2020-04-28 | Cabot Corporation | Self supporting areogel insulation |
| JP6195198B2 (en) * | 2014-03-31 | 2017-09-13 | パナソニックＩｐマネジメント株式会社 | Method for producing silica airgel |
| JP2018168206A (en) * | 2017-03-29 | 2018-11-01 | 住友理工株式会社 | Resin composition and method for producing the same |
| JP2022082299A (en) * | 2020-11-20 | 2022-06-01 | 国立研究開発法人物質・材料研究機構 | Heat insulating pipe |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20160010786A1 (en) | 2016-01-14 |
| EP2963327A1 (en) | 2016-01-06 |
| JPWO2014132655A1 (en) | 2017-02-02 |
| EP2963327A4 (en) | 2016-03-02 |
| WO2014132655A1 (en) | 2014-09-04 |
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